Process of producing polymers



Sept. 22, 1942.

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PROCESS OF PRODUCING POLYMERS Filed Sept. 8, I939 VAPOE our-4E $11. uL-UVT Flt/GRADE CATALYST Patented Sept. 22, 1942 2,296,399 PROCESS or raonucmc roummns Michael Otto, Ludwigshafen-on-the-Rhine, Germany, and Helmuth G. Schneider, Roselle, N. 1.,

assignors, by mesne assignments, to Jasco, In-

corporated, a corporation of Louisiana Application September 8, 1939, Serial No. 293,904

3 Claims. (Cl. 260-42) The present invention relates to an improved ,method for producing valuable polymers, and

more specifically polymers of isobutylene which may be used for various purposes. The invention will be fully understood from the following desoription.

Isobutylene can be polymerized to bodies high molecular weight at low temperatures of the order of -40 C. to -l00 C. For such process it is preferable to use catalysts, and among these the active halide catalysts such as boron fluoride and aluminum chloride or other catalysts may be used, but sulfuric acid and active clay catalysts are also applicable.

The polymers produced in this way are quite different from the well known dimers and trimers of isobutylene and range from very viscous oils to plastic solid or semi-solid rubbery materials which are all freely soluble in hydrocarbon oils. Liquid products may be used alone as lubricatin oils or they may be blended withnatural oils, while the plastic solid or semisolid polymers are of the greatest importance in thickening oils and simultaneously in raising pertures were required while to produce plastic solid polymers of progressively higher molecular weights, progressively lower temperatures were required.

By the means disclosed above, polymers of various molecular weights and thickening powers can be produced which are suitable-for blending agents with lubricating oils and other petroleum products. One advantage of these polymers is that while quite resistant to heat they tend to depolymerize and leave no solid carbonaceous residues. In general it is found that the heavier, that is the higher the molecular weight of the .product, the more readily it decomposes, and

since at the same time the. higher molecular weight product have the greatest thickening power, it is particularly desirable to limit the molecular weight range of polymers avoiding excessively high and low polymers, and increasing the yield of fractions whose molecular weights do not greatly difl'er from the average.

It has been found that the increased stability can be achieved by conducting the polymerization in the presence of materials which poison or inhibit the reaction. These poisons, which will be described below. do not, of course, prevent reaction under all conditions, but their presence requires a lower temperature to produce a polymer of a given average molecular weight than is required to produce a polymer of the same molecular weight range from isobutylene in the absence of such poison. In general, the required temperature reduction may be from 20 to say ('3. or even more-depending on the particular poison, its amount and other conditions such as the catalyst, the amount of inert diluent and the less than 1% 'and control must be very accurate for if too much be added solid polymers, especially having a molecular weight above 10,000, cannot be obtained with practically or commercially obtainable temperatures. Olfins of more than '2 carbon atoms other than isobutylene including'normal butylene or propylene and the like are also poisonous and are more useful because not so extreme in their action as sulfur for example. The proper amount of such poison ranges from say 10% to 25% so that this is easy to control and gives excellent commercial results. Small amounts of hydro-halides, such as hydrochloric or hydrofluoric acid, act as poisons for making solid high molecular weight polymers at low temperature, even though at higher temperatures they may even accelerate production of liquid oily polymers. Among the other materials which may be included in'the general scope of poisons are small amounts of lubricating oils or of aromatic hydrocarbons such as benzol or toluol, or normally liquid oleilns. In general it may be said that all sulfur, oxygen and nitrogen compounds having high dipole moments and forming stable complexes with Friedel-Crafts catalyst, and soluble in liquefied gaseous hydrocarbons are poisonous in the range of about 0.2-1.0%. This'applies to alcohols, esters, ethers,

' amines, nitrobenzene, etc.

In carrying out the'present process for polymerization in the presence of poisons it is necessary to have an accurate control over the nature and th 'e'amount of the poison present so that v The isobutylene may be prepared from any desired source, for example, from tertiary or isobutyl alcohol by dehydration or preferably from cracked light oils, for example, by polymerizing the isobutylene content into low molecular weight polymers with sulfuric acid of 50 to 70% strength. The polymer may be then separated from inert constituents and, depolymerized, for example, by heat in the presence of suitable catalysts so as to regenerate isobutylene, which is recovered as 'a fraction containing close to 90 or 100% isobutylene. 1

Such methods as have been disclosed above yield what might be termed moderately purified isobutylenes which may be further purified by careful distillation, washing with caustic soda or with sodium plumbite, or washingwith aqueo triethanol amine or similar substances to remove hydrogen sulfide andorganlc sulfur. Various combinations of these latter methods may be used depending upon the source of the isobutylene and, of course, on the particular impurities which it contains. Such secondary treatments are capable of producing what is termed a highly purified isobutylene.

To the highly purified isobutylene may then be added any particular poison desired, for example, as little as .05% of a light mercaptan or from .2 to 1% of 'tertiary butyl fluoride, but instead of any specific poison, mixtures of different poisonous materials may be used, for exam-- ple, a suitable volume of a partially purified isobutylene may be added to the highly purified product, or a smaller amount of the cracked light oils from which the purified isobutylene is derived, because such materials are rich in poisons, and are readily available.

The polymerization is preferably conducted in the presence of a diluent. This material should also be purified in much the same manner as discussed above, especially to. remove from its olefins and sulfur compounds. For this purpose,

hydrogenation is quite effective. The diluent can be used andreused many times and preferably consists of butane or propane or mixtures thereof with or without ethane or ethylene. It is, of course, quite possible to purify a fraction to the desired degree, leaving in it the desired amount of poison and while this is contemplated it is not a recommended and is much more difiicult than to purify completely and add. the required poison.

The polymerization itself may be conducted in batch or continuously-in any desired method with any of the catalytic materials described above and the temperature, as has been stated,

. is reduced so as to produce a polymer of the desired molecular weight range. It should be borne in'mind that, just as in the absence of poison,

the lower the temperature the higher will be the average molecular weight of the polymer mixture produced, and furthermore, that due to the presence of the poison a lower temperature must aaoaaoa when' poison 'ls present than would be necessary in the absence of the poison.

- the temperature may be definitely fixed and-uni- As stated above, the polymerization may be in batch orin a continuous flowing system, but in either case an adequate means should be applied for removal of heat which is liberated to a large extent. In order to obtain a uniform polymer, it is necessary to keep aclose control on the amount of the poison present, the amount of diluent' and the temperature at which the polymerization is effected. No particular means,

minor quantities 'of propane, propylene, pentane and amylene. This cut ordinarily contains from 10 to 20% of isobutylene.

A highly purified isobutylene fraction is obtained from C4 cut by absorbing theisobutylene in liquid condition in 50 to 65% sulfuric acid which is remarkably specific to isobutylene under those conditions. In this way the isobutylene is separated from other olefins and saturated hydrocarbons. butylene solution causes a polymerization to dimers and trimers of isobutylene and these may be separated from the acid. They are then cracked or depolymerized in the presence of active clays so as to yield a highly purified isobutylene containing from to of that material.

To 1 volume, for example, of this highly purified isobutylene is now added, say, 4 volumes of the raw C4 cut giving a mixture which will contain from about 20 to 40% of isobutylene and 10 to 20%,of other olefins, the balance, averaging 50%, being made up of saturated hydrocarbons. It is found that this fraction may be polymerized directly and requires no further diluent and the concentration of the other olefins is within the proper rangefor the most suitable control to bring about the poisoning effect disclosed above.

The product produced in the manner stated above is more stable than polymers obtained in,

and other products, for example, in proportion of .l to 5% or more and thereby effect a substantialthickening of the oil or, in other words', in-

crease in viscosity. They also produce at the same time an increase in viscosity index of the oil and are highly desirable for that reason. Stability can best be illustrated by loss in viscosity under severe working conditions; for example, the polymer blend in oil may becirculated through a small orifice under high pressure and the relative decreases in viscosity measure the relative stabilities of the different polymers. The oils also may be run under definite conditions between gear teeth so as to show a loss in visbe used to produce a'given molecular weight 75 cosity. Such tests are, of course, more severe either during or prior Gentle heating of the acid-isoas'oaaoe than the actual conditions of use so as to give an accelerated loss of viscosity. It has been found, as is indicated before and as will be specifically shown in the examples, that products produced in the presence of a poison are more stable. to working -conditions than those which are produced in the absence of a poison. Otherwise the present polymers appear to be identical with the polymers produced in the absence of poisons in that they are colorless, completely soluble with hydrocarbons and when decomposed by heat do not leave solid residues.

Example I In order to illustrate generally the effect of poisons on the polymerization of isobutylene a large quantity thereof was carefully purified particularly so as to be free-from sulfurs, halides and other poisons. To this highly purified isobutylene were then added small amounts of different poisonous materials and polymerization experiments were carried out under identical conditions with the several samples, including a blank on the purified isobutylene to which no poison had been added. In each case polymeri- 25 zation was conducted in the presence of three volumes of purified propane to one of isobutylene and a temperature of 50 C. was maintained during all runs. In the table the results are indicated showing the particular [poison used and the amount thereof, the yield of the polymer and its tetrahydronaphthalene number. The tetrahydronaphthalene number represents thickening power and is numerically equal to the viscos'ity' at 20 C. of a solution containing 2.8% of the particular polymer in tetrahydronaphthalene taking the viscosity of water at 20 C. as unity. This number represents therefore the thickening power of the polymer, the greater the number the greater being its thickening power. The average molecular weight of the polymer is proportional to the tetrahydronapthalene numher but since molecular weights are more difficult to obtain, tetrahydronaphthalene numbers are In the following test polymers of isobuylene were prepared on the one hand from highly purified materials as free as possible from poisonous agents, while on the other comparative tests poisons were present during the polymerization. In these pairs of comparative tests' (including one preparation where poison was used and one where no poison was present), temperatures of polymerization were in all cases below 40 C. and adjusted to give equal tetrahydronaphthalene numbers.

After the said polymers had been prepared, equal quantities (of the comparative polymers) were added to different samples of a lubricating oil having a viscosity of 66 Saybolt seconds at 210 F. The several samples were then run in a Chevrolet engine connected to a dynanometer 75 under as close to identical conditions as possible, each for-a period of four hours; At the end of these tests the loss in viscosity of the polymeroll blends were measured. The data is as follows: I Y

. Loss in viscosity, Saybolt %}3' Method of production g g fi seoopds 1 isobutylene polymerized in the presence oi pure propane. 7. 2 I 20, I 2.0 2 160 pts. isobutylene, 400 pts. propane, 30 pts. 0 fraction containing poisons reacted C 7.2 14 1.2 3 Isobutylene polymerized in the presence of ure propane. 7. 7 I 25 I 2. 0 4 160 pts. isobnty one, 400 pts. propane, 200 pts. 04 fraction containing poisons reacted at --C 7.7 8 1.4 5 Isobutylene polymerized in the presenceol pure propane 8. 7 I 37 I 3. 5 6 160 pts. isobutylene, 400 pts. propane, 25 pts. 0; fraction containing poisons reacted at 55 C 8. 7 20 2.3

v I Average data from a number of determinations.

" Nora-By polymerization at progressively lower temperatures,

Example II in the one case, using pure propane as a diluent and pure isobutylene, in the other case isobutylene obtained from a cracking op-' eration without subsequent purification sothat it contained natural poisonous impurities. For the diluent in the latter case propane was used which had been used and reused before for the same purpose. The blends of these polymers were made up as before and comparative tests were made on the Chevrolet engine for a period of four hours. Loss in viscosity is given in the table below:

t i if? 51 a o t Polymer and method of production 'I. N. of seonds atpolymer Impure isobutylene and reused propane. 7. 7 4. 0 0. 7 Pure isobutylene and pure propane 7. 7 25. 0 2.0

The latter is an average of a large number of tests.

Ewample'IV Tests similar to those given above were made showing that a 7.8 T. N. polymer prepared at 78 C. from materials containing poisons is more stable than a 6.5 T. N polymer prepared at 45? C; from highly purified materials.

Example V Tests similar to those above showed that a 5.25 T. N. polymer of isobutylene prepared at 80 C. in the presence of a crude refinery butane Example VI A highly purified isobutylene was polymerized at 78 C. with boron fluoride to a polymer having a molecular weight of about 70,000. This polymer was quite unstable to mechanical. working. On the other hand, a C4 cut, containing about 20% of isobutylene, when similarly polymerized 'at --'78 C. with boron fluoride, gave a polymer having a molecular weight of about 3,000.

In contradistinction to the above two tests, a mixture of 50% by volume of highly purified isobutylene and 50% by volume of C4 out when polymerized at -78 C. with boron fluoride, gave a polymer having a molecular weight of about 15,000. This polymer was very much more stable than the 70,000 molecular l weight polymer produced from the purified isobutylene alone and at the same time was sufficiently higher than the 3,000 molecular weight polymer produced from the 100% C4 cut that it had satisfactory viscosity and V. I, (viscosity index) improving properties for its use in lubricating oils. Polymers having a molecular weight as low as about 3,000 have, a slight vissocity-improvirig property in proportion to their molecular weight but do not substantially improve the V. I. of a lubricating oil to which it is added.

Example VII If the tests carried out in Example VI are carried out at a much lower temperature, e. g.

--103 C., as when liquefied ethylene is used as the refrigerant, the highly purified isobutylene produces a polymer having a molecular weight of about 150,000; but it is quite unstable to mechanical working; whereas, on the other hand,

in the presence of added C4 cut as a poison, the mixture produces a polymer having a molecular weight of about 70,000 which-is far superior in aaoaaca tance, but it will be'understood that the polyl mers may be used for any purpose and may be blended not only with lubricating oils, but with gasoline, kerosene, gas oils, waxes or greases. The invention is not to be limited by any theory of the blending qualities of such polymers, nor

to the efiect of the poisons, nor to any particular poison, nor to any theory of, the increased stability, but only to the following claims in which it is desiredto claim all novelty inherent in the invention.

This application is a continuation in part of application Serial No. 13,667 which was filed March 29, 1935.

We claim:

1. An improved method for producing high molecular weight viscous to plastic olefin'polymers of increased stability, which comprises. highly purifying an isobutylene fraction to remove therefrom all polymerization poisons, and adding thereto a major proportion of propane 1 and a controlled quantity of light cracked petrolet (2), liquid diluent, e g., liquefied propane,

from inlet (3), boron fluoride catalyst from inlet (4), and a proportioned amount of C4 cut con? taining normal butylenes from inlet (5). A draw-oil line. (7) may be'provided to remove the polymer product from the reactor, diluent may be recovered for reuse by leading vapors from the reactor. by way of line (8) thru a pressure control valve (9), then purifying the diluent vapors to a desired extent before they are liquefied and'recycled; I

The present invention is particularly adapted to the production, of solid polymers for blending lubricating oils so as to produce thickened oils of a higher viscosity index, and particularly in use in motor oils where stability is of imporieum fraction consisting essentially of hydrocarbons having 4 carbon atoms containing some isobutylene but also containing a substantial amount of normal butylenes as well as butanes, said amount of normal butylenes being-essentially less than the combined amount of isobutylene in the mixture formed andpolymerizing the I mixture with boron fluoride at a temperature below 40 C.

2. An improved process for producing viscous to plastic polymers of isobutylene of increased stability comprising concentrating and purifying isobutylene from a light cracked oilout rich in butane and butylene so as to obtain a fraction containing at least 90% isobutylene, adding this said purified cut and controlled quantity of the crude cut rich in butanes and butylenes so as to produce a mixture containing from 20 to 40% isobutylene and 10 to 20% of other olefins, the

proportion of isobutylene essentially preponderating over the proportion of other olefins and polymerizing said mixture with boron fluoride at a temperature below 40 C.

3. A method for polymerizing isobutylene t0 viscous polymers of increased stability, which comprises admixing purified isobutylene with other olefins having 3 to 5 carbon atoms per molecule such as are normally present in a cracked petroleum C4 out, and with an inert hydrocarbon diluent to form a reaction mixture containing a major proportion of said diluent mixture with boron fiuori'de as the catalyst at a temperature below 40 C.

MICHAEL o'rro. mom a. SCHNEIDER. 

